Ultraviolet light stabilizers

ABSTRACT

Ultraviolet light stabilized polymers having incorporated therein a stabilizing amount of a compound having the general formula:   WHEREIN R1 represents a hydrogen atom, an alkyl group or an acetyl group, R3R4, R5 and R6 are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group having up to 12 carbon atoms or an aryl group, n being 1 or 2 and, when n 1,R2 a hydrogen atom, an alkyl group, an acyl group having up to 20 carbon atoms, a substituted or non-substituted aroyl group, a phenoxy carbonyl group or a substituted or non-substituted benzene sulfonyl group and, when n 2,R2 is a sulfonyl, carbonyl or dioxaloyl group or a group having the formula   WHERE Z represents a phenylene group or an alkylidene group having up to 12 carbon atoms. Many of the compounds within this general formula are novel per se, and accordingly are claimed as such.

United States Patent 1 Havinga et a1.

[451 May 27, 1975 ULTRAVIOLET LIGHT STABILIZERS [75] Inventors:Reginoldus Havinga, Schalkhaar;

Pieter Dirk Swaters, Lochem, both of Netherlands [22] Filed: July 6,1973 [21] Appl. No.: 377,113

Related U.S. Application Data [62] Division of Ser. No. 67,588, Aug. 27,1970, Pat. No.

[30] Foreign Application Priority Data Aug. 28, 1969 Netherlands 6913138[52] U.S. Cl.... 260/45.85 N; 260/45.85 A; 106/178; 106/179 [51] Int.Cl. C08f 45/60; C08g 51/60 [58] Field of Search. 260/45.85 A, 45.85 N,471 R; 424/60; 106/178, 179

Primary ExaminerV. P. Hoke Attorney, Agent, or FirmStevens, Davis,Miller Mosher [57] ABSTRACT Ultraviolet light stabilized polymers havingincorporated therein a stabilizing amount of a compound having thegeneral formula:

-- NR R R wherein R represents a hydrogen atom, an alkyl group or anacetyl group, R R R and R are the same or different and each representsa hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or analkoxy group having up to 12 carbon atoms or an aryl group, n being 1 or2 and, when n 1,R a hydrogen atom, an alkyl group, an acyl group havingup to 20 carbon atoms, a substituted or nonsubstituted aroyl group, aphenoxy carbonyl group or a substituted or non-substituted benzenesulfonyl group and, when n 2,R is a sulfonyl, carbonyl or dioxaloylgroup or a group having the formula the compounds within this generalformula are novelper se, and accordingly are claimed as such.

11 Claims, No lDrawings 1 ULTRAVIOLET LIGHT STABILIZERS This is adivision of application Ser. No. 67,588, filed Aug. 27, 1970, now U.S.Pat. No. 3,809,707, issued May 7, l974.

The present invention relates to ultraviolet light stabilizers, that isto say, compounds which provide stabilization against the deteriorativeeffects of ultraviolet light, and provides a new class of such compoundsand processes for their preparation. The present invention also relatesto processes for preparing stabilized polymers by means of the novelcompounds according to the invention and of related compounds. Moreover,the invention relates to novel stabilized compositions.

It is known that polymers, such as polyethylene, polypropylene,polyisobutylene, copolymers of ethylene with higher alkenes such aspropylene and butylene or with vinyl acetate, polystyrene, polyvinylchloride, polyvinylidene chloride, copolymers of vinyl chloride withvinylidene chloride, polyvinyl acetate, polyester resins, polyurethanes,cellulose derivatives and other polymeric materials, may undergodegradation under the influence of ultraviolet light; this degradationtakes the form of deterioration of the physical properties and/or of thecolor of the polymers.

It has now been found that this degradation may be reduced, or avoided,by incorporating in the polymers a stabilizing amount of one or morepreviously unknown compounds according to this invention, having thegeneral formula:

wherein R represents a hydrogen atom, an alkyl group or an acetyl group,R and R are the same or different and each represents a hydrogen atom, ahalogen atom, a hydroxy group, an alkyl group having up to 12 carbonatoms or an aryl group, R and R are the same or different and eachrepresents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl oralkoxy group having up to 12 carbon atoms or an aryl group, n being 1 or2 and, when n 1, R is an acyl group having up to carbon atoms, asubstituted or non-substituted aroyl group, a phenoxy carbonyl group ora substituted or non-substituted benzene sulfonyl group and, when n 2, Ris a sulfonyl, carbonyl or dioxaloyl group or a group having the generalformula where Z is a phenylene group or an alkylidene group having up to12 carbon atoms.

Examples of novel compounds according to the above formula are:

l. phenyl-N-acetyl-anthranilate 2. phenyl-p-N-acetyl aminobenzoate 3.phenyl-p-N-acryloyl-aminobenzoate 4. phenyl-N-tosyl-anthranilate 5.phenyl-p-N-tosyl-aminobenzoate 6.p-tert.butylphenyl-N-acetyl-anthranilate 7.p-nonylphenyl-N-acetyl-anthranilate 8.p-chlorophenyl-N-acetyl-anthranilate 9.p-phenylphenyl-N-acetyll-anthranilate 10.m-hydroxyphenyl-N-acetyl-anthranilate l l.phenyl-N-nonanoyl-anthranilate l2. phenyl-p-N-nonanoyl-aminobenzoate l3.phenyl-N-stearoyl-anth:ranilate 14.m-hydroxyphenyl-N-nonanoyl-anthranilate l5.phenyl-m-N-acetyl-aminobenzoate l6. phenyl-N-benzoyl-anthranilate l7.phenyl-m-N-tosyl-aminobenzoate l8. m-0ctoxyphenyl-N-acetyl-anthranilatel9. phenyl-p-N-( 4-dodecylbenzene-sulfonyl- )aminobenzoate 20.phenyl-N-(4-chlorobenzoyl)anthranilate 21. phenyl-N-(4-cyanobenzoyl)anthranilate 22. phenyl-N-(2-methoxybenzoyl)anthranilate23. phenyl-N-(3-isopropylbenzoyl)anthranilate 24.phenyl-N-(4tert.butylbenzoyl)anthranilate 25.phenyl-N-methyl-N-acetyl-anthranilate 26.2-chloro-4-phenylphenyl-N-acetyl-anthranilate 27.2,4,5-trichlorophenyl-N-acetyl-anthranilate 28.p-nonylphenyl-N-tosyl-anthranilate 29.N,N'-bis(o-phenoxycarbophenyl)urea 30.N,N'-bis(o-phenoxycarbophenyl)oxalyl-diamide 31.N,N-bis(o-phenoxycarbophenyl)adipoyldiamide 32.N,N'-bis(p-phenoxycarbophenyl)sulfon-diamide 33.N,N'-bis(m-phenoxycarbophenyl)adipoyldiamide 34.N,N-bis(o-phenoxycarbophenyl)terephthaloyldiamide 35.N,N-bis(o-phenoxycarbophenyl)dodecanedioyldiamide 36.N,N-bis[2-(4-tert.butylphenoxycarbo)phenyl- ]adipoyl-diamide 37.N,N-bis[2-(4-nonylphenoxycarbo)phenyl]adipoyl-diamide 38.N,N-dimethyl-N,N'-bis(o-phenoxycarbophenyl- )adipoyl-diamide 39.phenyl-N,N-diacetyl-anthranilate 40. phenyl-N-phenoxycarbo-anthranilate41. p-tert.-octylphenyl-N-acetyl-anthranilate 42.p-dodecylphenyl-N-acetyl-anthranilate 43.N-(2-phenoxycarbo)phenyl-N-phenyl-urea 44.phenyl-N-hexyl-N-acetyl-anthranilate These compounds and the compounds45. phenyl-p.N,N-dimethyl-amino-benzoate 46.p-tert.butylphenyl-anthranilate 47. m-hydroxyphenyl-anthranilate 48.phenyl-N-methyl-anthranilate 49. phenyl-p-amino benzoate are referred tobelow, for convenience, by the numbers given in the left column.

The novel compounds of the general formula I may 0 be prepared, inaccordance with another aspect of this with a compound having thegeneral formula:

f HO g R I I I where R R R R and R have the meanings previously definedand A is a halogen atom or a hydroxy group, II preferably being anaminobenzoyl chloride, in an aqueous medium or an organic solvent,isolating the resultant compound of the formula:

and converting it into an acid amide or a sulfonamide of formula I.

The reaction is preferably carried out in the presence of an alkalinecompound at a temperature from 0C. to the boiling point of the solvent.Suitable solvents include benzene, dioxane, ethylene glycol dimethylether, chloroform, carbon tetrachloride, hexane and petroleum ether. Ifthe aminobenzoyl chloride and the phenol, i.e., the compounds offormulae II and III, are reacted in an organic solvent, pyridine,triethylamine and sodium carbonate may be used as alkaline compounds.The acid chloride, 11, may be added per se or wherein R, representshydrogen or alkyl. The reaction with a phenol may be carried out in asolvent, e.g., dioxane, acetone, dimethyl sulfoxide, ortetrahydrofurane, in the presence of an alkaline compound such aspotassium hydroxide or sodium hydroxide. While the carbon dioxide isescaping, compounds are formed having the general formula:

The compounds of the formulae IV and VI may be isolated from thereaction mixture by removing the solvent used, e.g., by decantation,filtering or distillation.

After purification by appropriate methods, these compounds may becharacterized by determining their physical constants such as meltingpoint, refractive index and their characteristic infrared absorptionbands.

Preferred reaction components which may be used include alkylated ornon-alkylated isatoic anhydrides, alkylated or nonalkylated aminobenzoicacids and aminobenzoyl chlorides, phenol, p-tert.-butylphenol,p-nonylphenol, p-chlorophenol, p-dodecylphenol, pphenylphenol,resorcinol and meta-octyloxyphenol.

The aminobenzoyl chlorides to be used may be obtained in known manner byreacting the corresponding acids with chlorinating agents, such as POClPCI PCl or SOCl The conversion of the compounds of the formulae IV andVI to the corresponding acid amides or sulfonamides may be carried outin a dry solvent, such as benzene, carbon tetrachloride, chloroform,petroleum ether, hexane, diethyl ether, ethylene glycol dimethyl ether,dioxane, ethyl acetate or n-butyl acetate, preferably in the presence ofan alkaline substance such as an amine, e.g. pyridine or triethylamine.

As acylating or sulfonating agents, there may be used acetyl chloride,acryloyl chloride, n-nonanoyl chloride, stearoyl chloride, benzoylchloride, substituted benzoyl chloride, p-toluene sulfonyl chloride,terephthaloyl chloride, sulfuryl chloride, oxaloyl chloride, succinoylchloride, dodecanoic dichloride, phosgene and phenylchloroformate.Ketene or acetic anhydride may also be used as acetylating agents. Afterpurification by appropriate methods, the acylated or sulfonatedcompounds may be characterized by determining their physical constantssuch as melting point or refractive index or their characteristicinfrared absorption bands.

In addition to the novel compounds according to the invention, phenylp-aminobenzoate, as described in Farmaco Ed. Sci. 12 (1957); phenylanthranilate, as described in US. Pat. No. 3,123,631; phenyl N-methylanthranilate, as described in J. Org. Chem. 24, 1214 (1959); phenylp-N,N-diethyl-aminobenzoate, as described in German Pat. No. 1,115,252;p-alkyl phenylanthranilate, as described in US. Pat. No. 2,776,959; andp-alkyl phenyl-p-aminobenzoate, as described in French Pat. No.1,253,378 may also be used in order to reduce or avoid the degradationof polymers by ultraviolet light. In this literature, it is notmentioned that these compounds may be used for avoiding degradation ofpolymers.

Consequently, the invention also relates to the stabilization ofpolymers with the aid of compounds having the general formula I, whereinR to R have the meanings given and wherein R and R can each additionallyrepresent an alkoxy group having up to 12 carbon atoms and wherein, whenn 1, R can additionally represent a hydrogen atom or alkyl group.

For use as U.V. absorbers, the compounds according to the presentinvention may be homogeneously incor- 5 rubs-CH porated in the polymersto be stabilized, if desired in the presence of other additives, e.g.plasticizers, pig- Yield 99.5% ments, heat stabilizers and lubricants,by known tech- (NH band Z a niques such as roller mixing. They arepreferably incor- Chm [R a (3:0 ester band porated in the polymer inamounts of 0.1 5% by amide b'and 'f l bl n h Starting from phenylanthranilate, in an analogous wlz g i es andlta 2 g l f e way, thefollowing compounds were obtained having vention. ere 1n t es e examp esan ta es re erence the general fomlula: 1s made to characteristicinfrared absorption bands, 1 5 these are expressed in microns. l o vnEXAMPLE I 849 g of isatoic anhydride (96%), 47.0 g of phenol, mm: 1.63 gof KOH and 500 ml of acetone were heated 2O under reflux for 2.5 hours.After cooling, the reaction TABLE 1 mixture was poured into water, theprecipitate was p 1 drawn off by suction and dried. 105.5 of phenylanthraacylating agent or nflate were obtained sulfonating agent solventbase product p-toluene sulfonyl chloride acetone pyridine 4) (tosylchloride) K 23 71C n-nonanoyl chloride chloroform (11) benzoyl chloride(16) (NHi band 2-82/2-92 stearoyl chloride (l3) Charact. 1R abs. 3Op-chlorobenzoyl pyridine (20) 1C=O ester band 5.90 chloridem-isopropylbenzoyl (23) chloride I H 21.3 g of the phenyl anthranilateobtained, 8.64 g of i 'gggg acetyl chloride (95%) and 400 ml of n-hexanewere p-cyanobenzoyl chloride (21) p-tert.butylbenzoy1 heated underreflux for 3 hours. After cooling the mixchloride ture the precipitatewas drawn off by suction. 25.4 g phenykhlomformale z aqphenyllsocyanatebenzene (43 of compound (1) were obtained, having the formula:

TABLE 2 Part 2 I characteristic physical IR absorption Product R2constants bands 4 so,c.,H.ci-|,- M.P. NH 3.01;

226229C. C O ester 5.89;

S O 7.41/8.62/10.85 (1 l) COC H -n liquid 11,, NH 2.99;

1.5453 C O ester 5.89; C =0 amide 5.91 (16) COC -H M.P. NH 3.00:

l66-l68.5C. C O ester 5.92;

C O amide 5.99 (13) COC, H n M.P. NH 2.99;

5153C. C =0 ester 5.90,

C O amide 5 90 (20) COC H ,Cl--p M.P. NH .03;

130.5132.5C. C O ester 5.99; C O amide 5.99 (23) COC6H4CH(CH M.P. NH2.99;

. --m 2 123-124.5c. c o ester 5.90;

.C O amide 5.99 (22) COC H OCH;,-o M.P. NH

9293.5C. C O ester 5 82,

C O amide 6 08 (21) COC H CNp M.P. NH 3.05;

166-168C. C O ester 5.96,

C O amide 6.00, C N 4.50 (24) COC H,C(CH -,);,-p M.P. NH 303;

114-117C C O ester 5.90, C O amide 6.01 CO.OCHH M.P. NH 3.04;

97.5-98C. C O ester 5 91, C O amide 5 71 (43) CONHCGHF, M.P. NH 304;

153-157C. O=Oester 5.86, C O amide 6.01

Compound (1) was also obtained by passing ketene into a solution ofphenyl anthranilate in n-butyl acetate at room temperature, yield 98%,or by heating in benzene with acetic anhydride, yield 76%.

EXAMPLE II 27.4 g of p-aminobenzoic acid were heated under reflux with100 ml of thionyl chloride for 2 hours and then the excess thionylchloride was distilled off under reduced pressure. The crudep-aminobenzoyl chloride was incorporated in 100 ml of dry benzene andadded to a suspension of 23.2 g of sodium phenolate in 250 ml of drybenzene. The mixture was heated under reflux for 2 hours and, aftercooling, treated with water and a saturated soda solution. After dryingthe benzene solution was saturated with hydrogen chloride gas. Theprecipitate of phenyl-p-aminobenzoate hydrochloride obtained wascentrifuged off. From the solid phase, 42.0 g of phenyl-p-aminobenzoatewas obtained with the aid of bicarbonate.

Yield 88% M. P. 168l71C.

(NH; band 288/295 Charact. 1R abs.

(C=O ester band 5.88

In an analogous way, phenyl-m-aminobenzoate was obtained.

Yield 85% M. P. 45.546.5C.

(NH band 289/296 Charact. 1R abs.

(C=O ester band 5.81

21.3 g of the phenyl-p-aminobenzoate so obtained were reacted withacetyl chloride in chloroform as solvent in theway described in ExampleI. 24.0 g of compound (2) were obtained, having the formula:

- 9 HT C O I CH Yield 94% M. P. 137C.

(NH band 2.97 Charact. 1R abs.

(C=O ester band 5.78 lC=O amide band 5.97

Starting from phenyl-m-aminobenzoate, in an analogous way, compound wasobtained, having the formula:

Yield M. P. 134-135C.

(NH band 2.94 Charact. IR abs.

lC=O ester band 5.82 (C=O amide band 5.90

Starting from the mor p-aminobenzoate, in an analogous way, thefollowing compounds were obtained having the general formula:

0 0 VIII TABLE 2 Part 1 acylating agent or sulfonating agent solventbase product acryloyl chloride chloroform 3) p-toluene sulfonyldiethylether pyridine 5) chloride n-nonanoyl chloride chloroform (12)p-dodecylbenzene ethylene glycol pyridine (19) sulfonyl chloridedimethyl ether p-toluene sulfonyl diethylether pyridine 17) chlorideTABLE 2 Part 2 characteristic physical IR absorption Product R constantsbands 3) COCHzCH M.P. NH 2.93;

1l5120C. C O ester 5 79;

. C O amide 5.99;

C O 6.10 5) SO C H CH M.P. NH 3.00;

226-229C. C O ester 5.81;

S O 7.45/8.60/10.92 12) COC,,H,-,n semi-solid NH 2.99;

product C O ester 5.80,

C O amide 6 O4 19) SO C H C H E, M.P. NH 3.02;

132-140C. C O ester 5.80;

S O 7.51/8.65/10.95 17) SO C H CH M.P. NH 3.07;

139-l40C. C O ester 5.75;

EXAMPLE III 8.1 g of isatoic anhydride, 11.0 g of p-nonylphenol and 1.1g of NaOH were heated under reflux in 50 ml of dioxane for 6 hours.After cooling, the reaction mixture was poured into water. 16.3 g ofp-nonylphenyl anthranilate were obtained, having the formula:

Yield 96% (NH band 2.85/2.94 Charact. IR abs.

(C=O ester band 5.89

Starting from other substituted phenols, in an analogous way, thefollowing compounds were obtained, having the general formula:

/R6 chloroform for 3 hours. After cooling and washing with water, thesolvent was distilled off. 13.4 g of compound o 7 were obtained, havinthe formula: R IX g 0 NR2 R3 R4 5 O .C9H19 TABLE 3 Part I substitutedphenol solvent anthranilate Yield 82% p-tert.butyldtoxanep-tert.butylphenylp 95 98C resorcinol dioxane m-hydroxyphenyl- (NH band3112 p-chlorodioxane p-chlorophenyl- Chara) [R gpnl y '4 h l 31 p g y pgg l) h I c=o ester band 5.90 -c oro -p enyioxane -c oro- -p eny -p enybd 5 9 2,4,5-trichlorodioxane 2,4,5-trichlorophenylam e anm-(n-)octoxydioxane m-(n-)octoxyphenyl- 1348110ct 9 M lfihen Startingfrom the substituted phenyl anthranilates, p'dodecy d'oxane pidodecy pany described in Example III, the following compounds were obtainedhaving the general formula: TABLE 3 Part 2 R h t t' 0 c arac ens tophysical IR absorption O R x R constants bands pC(CH3)3 M.P. 138-l40C.NH 285/293;

C O ester 5.88 -931 R R m-OH M.P. l71-l74C. NH 2.851295; 3 4

C O ester 5.98; OH 2.95 p-Cl M.P. 7980.5C. NH- 290/300;

c 0 ester 5.88 TABLE 4 p-C H M.P. l42-l45C. NH 2.85/2.95;

C O ester 5.94 Part 1 2---Cl-4C,;H,.- M.P. 107lO9C. NH 288/298;

C 0 651 -9 acylating agent or 2.4,5-Cl M.P. l29l3lC. NH2 2.83/293'.sulfonating agent solvent base product C O ester 5.85 a nq "n z 285/295;acetyl chloride chloroform 6) 1.5370 c O C O ester 5.90 may! m-m 10p-C(CH CH C(CH )3 M.P. 122 -l24 C NH: 288/297; acetyl chloride g C Oester 5.90 40 acetyl chloride 9) p l2 25 y P z n-nonanoyl chloridepyridine (14) C O ester .89 acetyl chloride acetyl chloride pyridine(27) ketene benzene (l8) EXAMPLE IV p-toluenesulfonyl chloride diethylpyridine (28) ether 14.5 g of p-nonyl phenyl anthranilate and 4.7 g of222:): chloirgform Py E25; acetyl chloride were heated under reflux inml of y TABLE 4 Part 2 R R physical characteristics lR product constantsabsorption bands 6) COCH pC(CH M.P. NH 3.03;

l63l65C. C O ester 5.90;

C O amide 5.98 (10) COCH m-OH M.P. NH 3.05;

l74l77C. C O ester 5 90,

C O amide 6 ()0 OH 3.05 8) COCH p-Cl M.P. NH 3.00

l07l l 1C. C O ester 5.89;

C O amide 5.92 9) COCl-L, p-C H M.P. NH 3.02;

l73.5175.5C. C O ester 5.90;

C O amide 5.99 (14) COC H, -n m-OH liquid NH 3.00;

C O ester 5.88; C amide 5.90; OH 3.00 (26) COCH 2Cl4-C.;H M.P. NH 2.99;

l42l44.5C. C O ester 5.85;

C O amide 5.92 (27) COCH,, 2.4,5Cl M.P. NH 2.99;

l40l43.5C. C O ester 5.88; C O amide 5.9l

TABLE 4 Part 2 Continued R2 R3 physical characteristics IR productconstants absorption bands (18) COCH, m-OC,,H, -r| M.P. NH 3.00;

4246C. C O ester 89,

C O amide 5 95 2s so,c,ii,cH,, pC,,H,., M.P. NH 3.09;

107l 10C. C O ester 5.93;

S O 7.50/8.60/l0.85 (41) COCHQ pC(CH;,) -,CH C(CH M.P. NH 3.03;

l68170C. C O ester 5.90,

C O amide 5 98 (42) COCH; pC H M.P. NH 3.00;

65-67C. C O ester 5.86,

C O amide 5.93

15 EXAMPLE V Li uid roduct n 1.5372 23.0 g of N-methyl isatoicanhydride, 12.2 g of pheq p L ester band 5,78 nol and 1.1 g of powderedNaOH were heated in 45 ml Chara IR b d 6 05 of dioxane for 4 hours at45C. After cooling, the reace tion mixture was poured into water. Theprecipitate was drawn off by suction, washed and recrystallized EXAMPLEVI from an ethanol-water mixture in a ratio of 4:1. 26.8 g ofphenyl-N-methyl anthranilate, having the formula below (R CH wereobtained:

Yield 91% M. P. 6667C.

(NH band 2.90 Charact. IR abs.

lC=O ester band 5.91

Starting from N-hexyl isatoic anhydride, in an analogous way,phenyl-N-hexyl anthranilate, having the formula XI (R G l-I wasobtained.

Liquid product m, 1.5660

(NH band 2.95 Charact. IR abs.

(C=O ester band 5.94

2.27 g of the phenyl-N-methyl-anthranilate obtained, 0.86 g of acetylchloride, 0.83 g of pyridine and 35 ml of dry chloroform were heatedunder reflux for 3 hours. After the solvent had been evaporated, washedand recrystallized from hexane, 2.47 g of compound (25) having theformula below (R, CH were obtained:

XII

R1 N (5) CH3 Yield 92% M. P. 176-178C.

lC=O ester band 5.78 Charact. IR abs.

(C=O amide band 6.05

Starting from phenyl-N-hexyl anthranilate, in an analogous way, compound(44) of formula XII (R C l-l was obtained.

Ketene was passed into a solution of 21.3 g of phenyl anthranilate,prepared in the way described in Example I, and 100 mg of p-toluenesulphonic acid in boiling toluene for 45 minutes. After the solvent hadbeen evaporated and recrystallized from a mixture of acetone and hexanein a ratio of 1:1, 13.3 g of compound (39) of forumula XII (R CH CO--)were obtained.

Yield 45% M. P. -87C.

(C =0 ester band 5.83 Charact. IR abs.

(c=o amide band 5.91

EXAMPLE VII 8.5 g of phenyl anthranilate, prepared in the way describedin Example I, 4.1 g of terephthaloyl chloride, and 4.8 ml of pyridinewere heated under reflux in chloroform for 4 hours. After cooling, theprecipitate was drawn off by suction, washed with hydrochloric acid andwater and recrystallized from chloroform. 10.1 g of compound (34 havingthe formula:

Charact. IR abs.

(C=O ester band 5.92 (C=O amide band 5.99

13 Starting from phenyl anthranilate, in an analogous way, the followingcompounds were obtained, having the general formula:

R Q- c' o x111 TABLE Part 1 acylating agent or sulfonating agent solventbase product phosgene diethyl ether pyridine (29) oxalyl chloridechloroform (30) adipoyl chloride dodecanoic dichloride (35) TABLE 5 Part2 R physical characteristic IR product constants absorption bands (29)CO M.P. NH 3.00;

l73-l77C. C 0 ester 5.90; C O amide 5.90 (30) CO.CO M.P. NH 3.05;

28l-283.5C. C O ester 5.84; (decomp.) C 0 amide 5.90 (31) --CO(CH ,COME. NH 3.00;

l26-l30C. C O ester 5.88; C O amide 5.92 (35) CO(CH ,CO M.P. NH 3.00;

5256C. C O ester 5.90;

C O amide 5.90

EXAMPLE VIII 6.81 g of phenyl-N-methyl anthranilate, prepared in the waydescribed in Example V, 2.75 g of adipoyl chloride and 5 ml of pyridinewere heated under reflux in 50 ml of chloroform for 4 hours. Aftercooling, the solution was washed with hydrochloric acid and then withwater to neutrality. After the solvent had been evaporated, petroleumether was added and then the precipitate formed was drawn off by suctionand dried. 5.50 g of compound (38) having the formula:

were obtained.

Yield 65% M. P. l40-l45C.

iC=O ester band 5.81 Charact. lR abs.

, lC=O amide band 6.08

14 EXAMPLE IX 5.0 g of phenyl-m-aminobenzoate, obtained in the waydescribed in Example II, 2.15 g of adipoyl chloride and 5 ml of pyridinewere heated under reflux in 50 ml 5 of chloroform for 4.5 hours. Aftercooling, the solution was washed with dilute hydrochloric acid andsubsequently with water and a sodium bicarbonate solution to neutrality.After the solvent had been dried and distilled off, the residue wasincorporated in benzene, decolorized with carbon and again precipitatedwith petroleum ether. After filtration, 4.25 g of compound (33) havingthe general formula below were obtained:

Yield M. P.

68% l53l56C. (NH band 2.95 Charact. lR abs.

(C=O ester band (C=O amide band Starting from phenyl-p-aminobenzoate andsulfonyl chloride, in an analogous way, compound (32) having theformula:

\ NH so were obtained.

M. P. 22l-224C.

:NH band IC=O ester band Charact. lR abs.

EXAMPLE X 3.39 g of p-nonylphenyl anthranilate, obtained in the waydescribed in Example Ill, 0.92 g of adipoyl chloride and 5 ml ofpyridine were heated under reflux in 30 ml of chloroform for 8 hours.After cooling and washing with water, the solvent was distilled off andrecrystallized from hexane. 2.84 g of compound (37) having the formulagiven below (R C9H19) were obtained.

Yield 72% M. P. l35-l38C.

(NH band 2.99 Charact. IR abs.

(C=O ester band 5.85 (C=O amide band 5.97

Starting from p-tert.butyl-phenyl-anthranilate, in an analogous way,compound (36) of formula XIV (R (CH C-) was obtained.

EXAMPLE XIV 100 g of unsaturated polyester resin, 2 g of a commerciallyavailable organic peroxide which is a mixture of benzoyl peroxide (50%by weight) and dimethylphthalate (Lucidol) and 0.2 g of compound (2)were mixed and poured into a sheet with a uniform thickness of 1 mm.This sheet was hardened for 2 hours at about 8090C. and subsequentlysubjected to ultraviolet radiation in a Xenotester for 2,000 hours.Next, the degradation was determined in the way described in Example X].This was 4. A sheet stabilized with compound (NH band 5 (l) and anon-stabilized sheet had a degradation of 4 Charact' IR abs' ic=0 est rband 5 s9 and 6 respectivelytc=o amide band 5:92 what is clalmed 1s:

l. A process for preparing a stabilized polymer, consisting essentiallyof incorporating in the polymer EXAMPLE XI a compound havlng the generalformula.

100 g of polyvinyl chloride, 35 g of dioctyl phthalate, 2 g of acommercially available barium-cadmium stabilizer which is abarium-cadmium-laurate-myristate mix- H R6 ture (Estabex BC-148) and 200mg of compound (6) o QR were mixed on a roll mixer at 180C. until ahomogene- R ous, colorless, transparent sheet was obtained. This 3 sheetwas pressed to a uniform thickness of 0.2 mm. Subsequently, it wassubjected to ultraviolet radiation 2 in a Xenotester for 2,000 hours.Next, the degradation was determined visually and rated according tonumeriwherein R represents a hydrogen atom, a lower alkyl cal scaleranging from 0 to 6, wherein the value 0 indigroup or an acetyl group; Ris a carbonyl or a cates that no degradation had taken place. grouphaving the formula:

In an analogous way, the stabilizing power of other compounds accordingto the present invention was de- C Z C termined. The compounds used andthe degradation II n measured are listed in Table 6. O 0

TABLE 6 Compound None (I) (4) (control) Degradation 6 1% 1% 2 1% 3 l 1%3 (l (1 3% 3 3 2% 2% 2 1% 1% l l 2 (2 (21) l l 3 l 1% 1% 2 EXAMPLE Xllwhere Z represents a phenylene group or an alkyli' 100 g of high-densitypolyethylene were mixed with dene group havmg up to carbon atoms; 250 mgof compound (7) and worked up on a roll 50 R and R are the same ordifferent and each repremixer into a colorless, transparent sheet at atempera- Sems a hydrogen atom a chlorme atom a hydroxy ture of 120C.This sheet was pressed to a uniform group an alky or alkoxy group havingP to 12 thickness of 0.2 mm and subsequently subjected to ulcarbon atomsa P y group, traviolet radiation in a Xenotester for 2,000 hours. As inamount Sufficient to stabilize the P y a measure of the degradation ofthe sheet, the carbonyl 5 A Process according to claim 1, comprisingincorcontent was determined. This content was 0.11. A pol'ating in the Py one or more auxiliary agentssheet bili d i h compound (42) d a 3. Aprocess according to claim 2, in which the auxilistabilized h er h d acarb l c t t f 0,12 d ary agents are plasticizers, pigments, heatstabilizers or 0.40 respectively. lubricants.

4. A process according to claim 1, in which the poly- EXAMPLE XIII meris polyvinyl chloride, polyethylene, polystyrene, or g of polystyreneand 0.2 g of compound l) were an Unsaturated polyester resin. mixed on aroll mixer at C. until a homogeneous, A Process according to Claim inwhich the p lycolorless, transparent sheet was obtained. This sheet meris polyvinyl chloride, polyethylene, polystyrene, or was pressed to auniform thickness of 0.2 mm. Subse- 5 an unsaturated polyester resin.

quently it was subjected to ultraviolet radiation in a Xenotester for2,000 hours. Next, the degradation was determined in the way describedin Example XI. This was 3. A sheet stabilized with compound (5) and anonstabilized sheet had a degradation of 4 and 6 respectively.

6. A process according to claim 3, in which the polymer is polyvinylchloride, polyethylene, polystyrene, or an unsaturated polyester resin.

7. A composition comprising a polymer and at least one compound usefulas an ultraviolet light stabilizer 10. A composition comprising apolymer and at least one compound useful as an ultraviolet lightstabilizer therefore, when made by a process according to claim 5.

11. A composition comprising a polymer and at least one compound usefulas an ultraviolet light stabilizer therefore, when made by a processaccording to claim 6.

2. A process according to claim 1, comprising incorporating in thepolymer one or more auxiliary agents.
 3. A process according to claim 2,in which the auxiliary agents are plasticizers, pigments, heatstabilizers or lubricants.
 4. A process according to claim 1, in whichthe polymer is polyvinyl chloride, polyethylene, polystyrene, or anunsaturated polyester resin.
 5. A process according to claim 2, in whichthe polymer is polyvinyl chloride, polyethylene, polystyrene, or anunsaturated polyester resin.
 6. A process according to claim 3, in whichthe polymer is polyvinyl chloride, polyethylene, polystyrene, or anunsaturated polyester resin.
 7. A composition comprising a polymer andat least one compound useful as an ultraviolet light stabilizertherefore, when made by a process according to claim
 2. 8. A compositioncomprising a polymer and at least one compound useful as an ultravioletlight stabilizer therefore, when made by a process according to claim 3.9. A composition comprising a polymer and at least one compound usefulas an ultraviolet light stabilizer therefore, when made by a processaccording to claim
 4. 10. A composition comprising a polymer and atleast one compound useful as an ultraviolet light stabilizer therefore,when made by a process according to claim
 5. 11. A compositioncomprising a polymer and at least one compound useful as an ultravioletlight stabilizer therefore, when made by a process according to claim 6.